Anti-allergen agent

ABSTRACT

Conventional tannic acid and polyphenol anti-allergen agents are known as anti-allergen agents capable of deactivating allergens such as mites and pollen, but these agents have inferior heat resistance and pose problems with coloration, discoloration and elution. The purpose of the present invention is to provide an anti-allergen agent that has excellent heat resistance, shows no coloration, and has excellent water resistance and workability. 
     It was discovered that using an inorganic substance having a high acid site concentration with acid site concentration being defined as the number of acid sites having a pKa of 4.8 or less, it is possible to realize an anti-allergen that manifests strong anti-allergen effects, has excellent heat resistance and water resistance, shows little coloration, and has excellent workability.

TECHNICAL FIELD

The present invention relates to an anti-allergen agent comprising an inorganic powder having a specific concentration of acid sites and to an anti-allergen composition and a product comprising the anti-allergen agent. The anti-allergen agent can impart an effect in reducing allergy-causing substances due to mites, pollen, etc. to fiber products such as clothing, bedding, and masks, filters used in air cleaners, air conditioners, etc., interior products such as curtains, carpets, and furniture, automotive interior materials, etc. by means of spraying or coating, or by fixing to a surface layer of building materials such as wallpaper and flooring materials.

BACKGROUND ART

In recent years, the number of people suffering from allergic diseases such as pollen allergy due to Cryptomeria japonica pollen, etc., bronchial asthma due to house dust caused by mites, etc., hay fever, allergic rhinitis, and atopic dermatitis has been increasing and is becoming a serious problem. As methods for treating such allergic diseases, there has been great progress as a result of the development of the series of medicinal agents called anti-allergic drugs, and steroids for inhalation or external use, but these are still only symptomatic treatments and not curative treatments.

Furthermore, a miticide, etc. is generally used for the eradication of house dust mites, but Dermatophagoides farinae, Dermatophagoides pteronyssinus, etc. in house dust have the characteristics that not only the mites' bodies but also the feces and remains thereof cause an allergy reaction, and since fine allergen particles are gradually released as the remains decompose after death, merely killing mites cannot inactivate the allergens. Moreover, masks are used for preventing inhalation of the pollen of Cryptomeria japonica, etc., but since the allergen activity of pollen attached to the mask does not disappear, there is a risk of inhalation when the pollen is scattered again.

Because of such problems, in order to alleviate the symptoms of an allergic disease or prevent new sensitization, it is necessary to remove allergens, which are the substances causing allergic symptoms, from a living space before they are inhaled into the human body, or render them harmless by modification.

As a method for removing an allergen without using a medicinal agent, there is a method in which the amount of allergen is lessened by physically removing floor-deposited dust or air-suspended dust by suction with a vacuum cleaner or an air purifier. However, a large amount of allergen sucked up by a vacuum cleaner is simply stored in a dust bag, and it can be expected that there will be a risk of rescattering the allergen when disposing of the dust bag. Furthermore, it is difficult to completely remove a fine particulate substance by removal using an air purifier, and there is a risk of it being rescattered.

Consequently, an anti-allergen agent that inactivates a harmful allergen to make it harmless by the action of adsorption on or covering of a reactive site of the allergen with an antibody has recently been proposed. For example, methods employing tannic acid are disclosed in Patent Documents 1 and 2, Non-Patent Document 1, etc., and Patent Document 3 discloses a polyphenol such as gallic acid and tea extract, which is an analogous compound to tannic acid. However, an organic allergen-reducing agent such as tannic acid is chemically unstable, and there are the problems that when it is attached to fiber or fiber products, coloration might occur or it might change in color over time, or it might bleed out to the environment due to water, oil, solvent, or washing, thus causing coloration of clothing or skin irritation. For example, Patent Document 1 discloses that tannic acid can be removed by distilled water, and it is thus clear that when a fiber treated with tannic acid is washed repeatedly the tannic acid is lost. Therefore, there is a problem with the use thereof as an anti-allergen agent in fiber or fiber products that have a possibility of being washed or being in direct contact with the skin, and there is the drawback that application targets are limited for fiber products that are exposed to view because of problems with color tone, heat resistance, or durability. As one that improve the above defects, an anti-allergen agent comprising an inorganic substance has been proposed. Patent Document 4 discloses that allergen can be adsorbed using an inorganic substance such as activated charcoal, but a substance, such as activated charcoal, that exhibits adsorption based on the principle of physical adsorption due to it having a large porous specific surface area usually shows low anti-allergen adsorption performance and is black, and its application is therefore limited, which is a problem. Furthermore, Patent Document 5 discloses that, among inorganic substances, one having a high solid acid strength has excellent anti-allergen activity. However, even with substances showing the same level of solid acid strength, the allergen inactivation performance can vary to a great extent in practice, and one having higher solid acid strength does not always exhibit better anti-allergen activity. Furthermore, it has become clear that when a fiber is processed in an aqueous system using a solid acid having very high solid acid strength, metal sections of processing equipment might be corroded, which is a problem.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: JP-A-61-44821 (JP-A denotes a Japanese unexamined     patent application publication) -   Patent Document 2: JP-B-2-16731 (JP-B denotes a Japanese examined     patent application publication) -   Patent Document 3: JP-A-6-279273 -   Patent Document 4: JP-A-2002-167332 -   Patent Document 5: WO2009/044648

Non-Patent Documents

-   Non-Patent Document 1: ‘Sosetsu Tanninnikansuru Saikinnokenkyu’     (Review of Recent Research into Tannin), Yakugaku Zasshi, 103 (2),     125-142 (1983)

SUMMARY OF INVENTION

In light of the above circumstances, the object of the present invention is to provide an anti-allergen agent comprising an inorganic substance that has high anti-allergen performance and excellent heat resistance and ease of processing, causes hardly any coloration, and is not leached out by water, and is preferably an anti-allergen agent that causes hardly any change in color or corrosion of equipment when used as a coating composition or a resin composition, and to provide an anti-allergen composition and an anti-allergen product using same.

As a result of an intensive investigation by the present inventors in order to solve these problems, it has been found that an inorganic powder having a concentration of acid sites with a pKa of no greater than 4.8 of at least 0.001 mmol/g exhibits high anti-allergen activity, and the present invention has thus been accomplished. The present invention is an anti-allergen agent comprising an inorganic powder having a concentration of acid sites with a pKa of no greater than 4.8 of at least 0.001 mmol/g, and an anti-allergen composition and an anti-allergen product using the anti-allergen agent.

DESCRIPTION OF EMBODIMENTS

The present invention is explained below.

The concentration of acid sites referred to with respect to the anti-allergen agent of the present invention is the number of acid sites or acidic centers on a solid surface and is usually expressed as a number of moles or a number per unit weight or unit surface area of a solid. The acid strength of an acid site used for calculation of the concentration of acid sites can be expressed as pKa. The acid strength represents the strength of the property of an acid site on a solid surface of donating a proton to a base or the property of accepting an electron pair from a base; the smaller the pKa of an acid site, the stronger the property of donating a proton to a base or the property of accepting an electron pair from a base, and the higher the ability to inactivate an allergen protein by adsorbing it.

However, usually, while one acid site is adsorbing one allergen protein it cannot adsorb another allergen protein; even when each acid site has a high acid strength, if the number of acid sites, that is, the concentration of the acid sites, is low, adsorption soon reaches saturation and a sufficient anti-allergen effect cannot be exhibited. When there is a large amount of allergen protein, if the quantity thereof adsorbed, that is, the concentration of acid sites, is high, a high anti-allergen effect is exhibited.

On the other hand, when the acid strength of an acid site is small, that is, when the pKa is large, the strength of the property of donating a proton to a base or the property of accepting an electron pair from a base is weakened; when the pKa is too large, the ability of each acid site in adsorbing an allergen protein and inactivating it becomes low, and even if the number of acid sites, that is, the concentration of the acid sites, is large, it becomes difficult for allergen protein to be fully adsorbed. Although this balance also depends on the structure of the allergen protein and the compatibility between a base and an acid site, as a result of examining representative allergen proteins in the present invention, when an inorganic substance having an acid site has a pKa for the acid site of no greater than 4.8, it exhibits an inactivating effect toward any allergen protein, and the number of acid sites, that is, the concentration of acid sites, correlates with the anti-allergen effect irrespective of the type of allergen protein. That is, it has been found that a measurement of the concentration of acid sites of a solid acid having a pKa for the acid sites of no greater than 4.8 can be used as an indicator for the anti-allergen performance of the substance.

More specifically, with regard to the anti-allergen agent of the present invention, the number of acid sites of an inorganic substance powder having a pKa for the acid sites of no greater than 4.8 is defined as the ‘concentration of acid sites’ in the present invention; the larger this value, the higher the anti-allergen performance, and the more preferable it is as an anti-allergen agent. Specifically, one having a concentration of acid sites of at least 0.001 mmol/g is preferable. There is no upper limit for the concentration of acid sites that should not be exceeded, but since no inorganic substance powder that exceeds 10 mmol/g is usually known as a specific material, the upper limit is usually no greater than 10 mmol/g.

With regard to measurement of the number of acid sites having a pKa of no greater than 4.8, by applying a titration method using an indicator that corresponds to a pKa of 4.8, the total of all acid sites having a pKa of no greater than 4.8 can be measured, and this value is defined as the concentration of acid sites having a pKa of no greater than 4.8. In the present invention, the concentration of acid sites is preferably at least 0.01 mmol/g, and more preferably at least 0.05 mmol/g. In particular, an inorganic substance having a concentration of acid sites of at least 0.05 mmol/g has an excellent anti-allergen effect and exhibits a high effect for various allergen substances.

The concentration of acid sites of a powder may be determined by measuring the amount of base that reacts with the powder. There are methods in which measurement is carried out in a liquid phase or a gas phase; a titration method is known as a method for measurement in a liquid phase, and there is known as a method for measurement in a gas phase a gas chemical adsorption method such as a method in which the difference between the amount of He or hydrogen gas adsorbed and desorbed and the amount of a basic gas adsorbed and desorbed is measured. The reaction between an anti-allergen agent and an allergen in the present invention is a reaction employing a liquid as a medium, and measurement by a titration method in a liquid phase is therefore suitable.

A method for measuring the concentration of acid sites of an inorganic powder by a titration method in a liquid phase is as follows.

An inorganic powder dispersed in a nonpolar solvent is titrated using n-butylamine, and the end point of the titration is confirmed by a change in color of an indicator. The indicator prior to reaction exhibits a color due to its base form, but when it is adsorbed on an inorganic powder it exhibits a color due to it being in a conjugate acid form. The amount of n-butylamine titrated that is required to change the color due to the conjugated acid form to the color due to the base form is used to determine the concentration of acid sites. One acid site of a solid corresponds to one n-butylamine molecule. Since the base for titration needs to replace an indicator bound to an acid site of the solid, the basicity thereof should be stronger than the basicity of the indicator. In a usual titration method, when an indicator is first added to an inorganic powder/benzene dispersion, the indicator exhibits the acid color due to the solid acidity, and it is preferable to leave it for a sufficient time until a reaction is completed. Subsequently, dropwise addition of n-butylamine is started, and the concentration of acid sites is calculated from the amount of n-butylamine when the color of the indicator returns to its original basic color.

More specifically, 0.5 g samples of an inorganic powder are placed in 20 mL sample vials, 10 mL of benzene is added to each thereof, and the vial is lightly shaken. 20 stepped amounts of 0.1 N n-butylamine are added thereto, and stirring is carried out by an agitator. 24 hours thereafter, 0.5 mL of a 0.1% methyl red indicator solution is added thereto, and change in color of the indicator is examined. The amount of n-butylamine added in the system in which the largest amount of n-butylamine has been added among those systems where no change in color of the indicator is observed is defined as the mount of base that has reacted with the acid sites, and is expressed as the concentration of acid sites (mmol/g). Here, N is also called normality, and is a commonly used unit for a person skilled in the art, being defined by normality=molar concentration×acid value of one molecule.

An inorganic substance having a high concentration of acid sites is a solid having many acid sites on the surface. Specific examples of inorganic substances having a high concentration of acid sites include, but are not limited to, amorphous magnesium silicate, α-type zirconium phosphate, layered titanium phosphate, activated alumina, and activated titania.

In order for the anti-allergen agent of the present invention to be applied to processing with various materials and configurations, the average particle size is preferably 0.01 to 50 μm, and more preferably 0.02 to 20 μm. A powder having an average particle size of at least 0.01 μm has the advantage of ease of handling since it does not easily reaggregate. Furthermore, when dispersed in a binder, etc. and post-processed with a fiber, particles having an average particle size of no greater than 50 μm are preferable since they have good dispersibility, do not degrade the texture of a fiber, and do not easily cause thread breakage when kneaded with a fiber. An average representative value for the particle size may be measured by means of a laser diffraction particle size distribution analyzer, etc., and a median diameter analyzed on a volumetric basis may be used as a representative value for the particle size.

There is no restriction on the color tone of the anti-allergen agent in the present invention, but in order to apply it to processing with various materials and configurations, white or a pale color having high lightness is preferable. The lightness is preferably at least 60 as an L value when measured using a colorimeter.

Furthermore, the inorganic substance forming the anti-allergen agent in the present invention preferably has an acid strength pKa of no greater than 1.5. This is because high anti-allergen properties are exhibited if the acid strength as a solid acid is high in addition to there being a high concentration of acid sites. The acid strength of the anti-allergen agent referred to in the present invention is the ability of an acid site of the anti-allergen agent surface to donate a proton to a base or the ability thereof to accept an electron pair from a base. Measurement of acid strength may be carried out by a method employing an indicator. Selecting an appropriate indicator as a base enables acid strength to be measured in terms of the ability to convert the base form of the indicator into its conjugate acid form.

Examples of indicators that can be used in measurement of acid strength and (pKa values) include methyl red (+4.8), 4-phenylazo-1-naphthylamine (+4.0), dimethyl yellow (+3.3), 2-amino-5-azotoluene (+2.0), 4-phenylazo-diphenylamine (+1.5), 4-dimethylaminoazo-1-naphthalene (+1.2), crystal violet (+0.8), p-nitrobenzeneazo-p′-nitro-diphenylamine (+0.43), dicinnamylacetone (−3.0), benzalacetophenone (−5.6), and anthraquinone (−8.2). Use of such various acid-base conversion indicators whose acid strength (pKa) is known enables acid strength to be measured. The lower the pKa of the indicator whose color is changed, the higher the acid strength.

A method for measuring the acid strength of an inorganic solid acid employing the above-mentioned indicators is as follows.

0.1 g of a solid acid is weighed in a test tube, and 2 mL of benzene is added thereto and mixed by gently shaking. Two drops of a 0.1% benzene solution of an indicator (for crystal violet, a 0.1% ethanol solution instead of a benzene solution) are added thereto and mixed by gently shaking, and change of color is examined. The acid strength of the solid acid is equal to or less than the highest acid strength (that is, the lowest pKa value) where change in color of the indicator is confirmed and greater than the lowest acid strength (that is, the highest pKa value) where change in color of the indicator is not confirmed, and the pKa value of the inorganic solid acid is expressed as (highest pKa value where change in color is not confirmed) to (lowest pKa value where change in color is confirmed). Furthermore, where there is no appropriate indicator for showing a lower limit, it is generally expressed as being equal to or less than (lowest pKa value where change in color is confirmed), and when there is no appropriate indicator for showing an upper limit, it is expressed as being greater than (highest pKa value where change in color is not confirmed).

The anti-allergen effect of the inorganic substance in the present invention is easily exhibited when it has a defined moisture content. The water content in the inorganic substance is preferably at least 0.5 wt %, more preferably at least 2 wt %, and yet more preferably at least 10 wt %. An inorganic substance having hygroscopicity can retain moisture in the inorganic substance even when it is mixed with another material or the humidity of the atmosphere changes, and it is excellent in terms of having in the inorganic substance itself the moisture necessary to inactivate an allergen.

The anti-allergen effect of the present invention is evaluated by a sandwich ELISA method, which is widely known as a method for detecting/quantifying an antigen, and can be expressed as the percentage allergen inactivation (units: %) shown in <Equation 1>. The initial amount of allergen means the amount of allergen used in an ELISA evaluation and evaluated without using a sample, and the amount of allergen remaining means the amount of allergen after contacting a sample. Furthermore, the allergen inactivation referred to in the present invention means suppression of a reaction between the allergen and a specific antibody, and the higher the percentage allergen inactivation, the more preferable it is. Specifically, the percentage allergen inactivation is preferably 90% or greater, and more preferably 99% or greater.

Percentage allergen inactivation=(1−amount of allergen remaining/initial amount of allergen)×100(%)  <Equation 1>

The configuration of use of the anti-allergen agent of the present invention is not particularly limited, and it may be mixed with another component or compounded with another material as appropriate according to the intended application. For example, it may be used in various configurations such as powder, powder-containing dispersion, powder-containing particles, powder-containing paint, powder-containing fiber, powder-containing paper, powder-containing plastic, powder-containing film, and powder-containing aerosol and, furthermore, if necessary various types of additives and materials such as a deodorant, an antimicrobial agent, an antifungal agent, a flame retardant, a corrosion inhibitor, a fertilizer, and a building material may be used in combination. Furthermore, addition to a material for which there is a possibility of it being in human contact, such as for example resin, paper, plastic, rubber, glass, metal, concrete, timber, paint, fiber, leather, or stone, makes it possible to inactivate allergens in a living space.

Among these application methods, use of the anti-allergen agent of the present invention as a coating composition containing a fixing agent (binder) is preferable. This coating composition may contain an additive in addition to the binder, and the coating composition may be diluted with a solvent or water before processing therewith a product with various types of shapes. On the one hand the larger the anti-allergen agent/binder solids content ratio by weight in the coating composition of the present invention, the easier it is for an effect to be exhibited, but on the other hand the larger the binder solids content ratio by weight, the more strongly the anti-allergen agent is fixed and the harder it is for the power to fall off. Therefore, the anti-allergen agent/binder solids content ratio by weight in the coating composition containing the anti-allergen agent is preferably 90/10 to 30/70, and more preferably 80/20 to 50/50.

When the coating composition is used by dilution, from the viewpoint of ease of dispersion and good storage stability, the concentration of the anti-allergen agent contained in the composition is preferably 0.5 to 50 mass %, and more preferably 1 to 30 mass %. Since an anti-allergen effect is usually exhibited by contact between an anti-allergen agent and an allergen on the surface of a product with various types of shape, fixing an anti-allergen agent to the surface of a product by means of the coating composition is preferable to it being used in the entire interior of a product because a large effect can be obtained with a smaller amount of anti-allergen agent.

The binder used in the coating composition of the present invention includes those below. That is, there are a natural resin, a natural resin derivative, a phenolic resin, a xylene resin, a urea resin, a melamine resin, a ketone resin, a coumarone/indene resin, a petroleum resin, a terpene resin, cyclized rubber, chlorinated rubber, an alkyd resin, a polyamide resin, polyvinyl chloride, an acrylic resin, a vinyl chloride/vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, chlorinated polypropylene, a styrene resin, an epoxy resin, urethane and cellulose derivatives, etc. Among them, an acrylic resin, polyvinyl chloride, and a vinyl chloride/vinyl acetate copolymer resin are preferable, and an emulsion type resin is particularly preferable since it is less polluting and easy to handle.

Furthermore, examples of those that can be used as an additive include a pigment such as zinc oxide or titanium oxide, a dye, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a foaming agent, an impact modifier, glass fiber, a lubricant such as a metallic soap, a desiccant, an extending agent, a coupling agent, a nucleating agent, a flowability improving agent, a deodorant, wood flour, a fungicide, an antifoulant, a corrosion inhibitor, a metal powder, a UV absorber, and a UV shielding agent.

As a method for processing a fiber using a coating composition comprising the anti-allergen agent of the present invention, there is a method in which a fiber or a fiber product is coated with, immersed in, or sprayed with the coating composition as it is or a diluted liquid thereof. There is no limitation to the fiber that can be processed, and examples thereof include natural fibers such as cotton, silk, and wool, synthetic fibers such as polyester, nylon, and acrylonitrile, semi-synthetic fibers such as triacetate and diacetate, and recycled fibers such as viscose rayon, and a composite fiber employing two or more types of the above fibers may be used. Moreover, use with a nonwoven fabric employing polyethylene, polypropylene, etc. is also possible. A method for processing a fiber or a fiber product with the anti-allergen agent of the present invention is not particularly limited; there are an immersion treatment, a printing treatment, a spraying treatment, etc., and processing is completed by drying the fiber containing the composition. A drying method may employ any method such as natural drying, hot air drying, or vacuum drying, and an anti-allergen agent may be fixed to a fiber preferably by a drying method involving heating at 40° C. to 250° C., and preferably 50° C. to 180° C., for 1 min. to 5 hours, and preferably for 5 minutes to 3 hours.

When the amount of anti-allergen agent of the present invention attached to a fiber or a fiber product is at least 0.1 g per m² of the fiber or fiber product, an effect can be exhibited. On the other hand, in order to prevent the physical properties and texture of the fiber or fiber product from being degraded, it is preferably no greater than 20 g/m², and is more preferably 1 g to 10 g/m².

When the pH of the coating composition comprising the anti-allergen agent of the present invention is too low, metal of production equipment might be corroded, a processing solution might be degraded, or its stability might be impaired, whereas when the pH is too high, the solid acid is neutralized and the anti-allergen effect might be decreased; when the coating composition is an aqueous system, etc. and measurement of pH is possible, the pH is preferably at least 3 but no greater than 9. The main factors for determining the pH of a coating composition are the same as those for the pH of an aqueous dispersion of an inorganic powder and are greatly influenced by the pKa of the solid acid, but they are also influenced by the concentration of acid sites, the solubility or hydrophilicity of the anti-allergen agent itself, or a component, other than the anti-allergen agent, forming the coating composition, and it is difficult to predict the pH; when the pH is too low, the dispersion itself containing the coating composition becomes acidic, if it becomes attached to a metal section of processing equipment, rust might be formed, and the effect of a dispersant might be degraded, thus causing the dispersion to form a precipitate.

Furthermore, when the coating composition comprising the anti-allergen agent of the present invention is a nonaqueous system or is used as a paint comprising various types of paint component or when it is used as a resin composition comprising the anti-allergen agent, a metal section with which it is in contact might be similarly corroded, or change in color of a resin might occur; it has been found that, in a test as an aqueous dispersion system, one that gives a pH in a fixed range is preferable since hardly any rust or change in color occur. As such a test as an aqueous dispersion system, a method in which an anti-allergen agent is dispersed in water and its pH is measured is an easy method. For example, an anti-allergen agent is dispersed in deionized water at 5 wt %, the pH after stirring at 25° C. for 5 min. by means of a stirrer may be measured using a glass electrode pH meter, and the pH thus obtained is preferably at least 3 but no greater than 9. A coating composition, a paint, a resin, etc. employing such an anti-allergen agent is preferable since hardly any metal corrosion or change in color occurs. Since a paint is a composition for the purpose of coating, it is one type of coating composition, but in particular a coating composition that is not only for the purpose of fixing a functional component such as an anti-allergen agent but also for exhibiting weatherability or protection or for the aesthetic appearance of an article surface while a coating itself formed by curing the composition has a certain strength is called a paint.

The anti-allergen agent of the present invention can be used by adding it to a paint. The paint may contain various types of additive. Examples of a resin component of the paint include oils such as soybean oil, linseed oil, safflower oil, and castor oil, natural resins such as rosin, copal, and shellac, processed resins such as a chroman resin and a petroleum resin, synthetic resins such as an alkyd resin, an acrylic resin, an epoxy resin, a polyurethane resin, a vinyl chloride resin, a silicone resin, and a fluorine resin, rubber derivatives such as a chlorinated rubber and a cyclized rubber, and cellulose derivatives such as cellulose nitrate (lacquer) and acetyl cellulose. Examples of a pigment of the paint include colorant pigments such as (white) titanium, (black) carbon, (brown) red iron oxide, (vermillion) chrome vermillion, (blue) Prussian blue, (yellow) chrome yellow, and (red) iron oxide, extender pigments such as calcium carbonate, talc, and baryta powder, anticorrosive pigments such as red lead, lead suboxide, and lead cyanamide, and functional pigments such as aluminum powder and zinc sulfide (fluorescent pigment). Examples of paint additives include a UV-curing agent, a plasticizer, a dispersant, an antisettling agent, an emulsifying agent, a thickener, an antifoaming agent, an anti-mold agent, a preservative, an antiskinning agent, a desiccant, an antidrip agent, a delustering agent, an antistatic agent, a conductive agent, a flame retardant, and an antigraffiti agent. Examples of a solvent of the paint include water, an alcohol, and a thinner such as a paint thinner, a lacquer thinner, or a thinner for a polyurethane resin, and a paint may be prepared by combining the above.

As a method for processing a substrate with a paint comprising the anti-allergen agent of the present invention, a pre-produced substrate may be coated with a paint as it is or as a liquid after dilution by means of a brush application technique, a roller technique, a spraying technique, a trowel application technique, etc. Furthermore, the applied paint may be cured by exposure to UV. There are various types of substrate that can be processed, examples thereof including various types of plastics such as polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, and cellophane, a vinyl chloride sheet, a jointing compound such as a modified silicone or urethane, metal, ceramic siding, porcelain, stone, earthenware, glazed tiles, marble, granite, and glass.

When the anti-allergen agent/paint solids content ratio by weight in a paint comprising the anti-allergen agent of the present invention is at least 10/90, a clear effect can easily be exhibited. Furthermore, in terms of economic reasons or the physical properties and texture of a substrate to be painted not being degraded, or in terms of the physical properties and function of the paint not being greatly impaired, it is preferably no greater than 50/50. Therefore, the anti-allergen agent/paint solids content ratio by weight in a paint comprising the anti-allergen agent of the present invention is preferably 10/90 to 50/50, and more preferably 20/80 to 40/60.

The anti-allergen resin composition may easily be obtained by combining the anti-allergen agent of the present invention with a resin. The type of resin that can be used is not particularly limited; any of a natural resin, a synthetic resin, and a semi-synthetic resin may be used and, moreover, either of a thermoplastic resin or a thermosetting resin may be used. Specifically, the resin may be any of a resin for molding, a resin for fiber, and a rubber-form resin, and examples thereof include resins for molding or fiber such as polyethylene, polypropylene, vinyl chloride, an ABS resin, an AS resin, an MBS resin, a nylon resin, polyester, polyvinylidene chloride, polystyrene, polyacetal, polycarbonate, PBT, an acrylic resin, a fluorine resin, a polyurethane elastomer, a polyester elastomer, melamine, a urea resin, a tetrafluoroethylene resin, an unsaturated polyester resin, rayon, acetate, acrylic, polyvinyl alcohol, cupra, triacetate, and vinylidene, and rubber-form resins such as natural rubber, silicone rubber, styrene butadiene rubber, ethylene propylene rubber, fluorine rubber, nitrile rubber, chlorosulfonated polyethylene rubber, butadiene rubber, synthetic natural rubber, butyl rubber, urethane rubber, and acrylic rubber. Moreover, in addition to a resin component, various types of additives may be added. Examples of additives that can be used include a pigment such as zinc oxide or titanium oxide, a dye, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a foaming agent, an impact modifier, glass fiber, a lubricant such as a metallic soap, a desiccant, an extending agent, a coupling agent, a nucleating agent, a flowability improving agent, a deodorant, wood flour, a fungicide, an antifoulant, a corrosion inhibitor, a metal powder, a UV absorber, and a UV shielding agent, and any thereof may be used preferably.

A method for producing a resin composition by combining the anti-allergen agent of the present invention with a resin may employ any known method. For example, there are (1) a method in which an attachment agent for making it easy for an anti-allergen agent powder to become attached to a resin or a dispersant for improving the dispersibility of an anti-allergen agent powder is used, and a pellet-form resin or a powder-form resin is directly mixed by a mixer, (2) a method in which mixing is carried out as described above, molding into pellets is carried out using an extruder, and the resulting molding is then combined with a pellet-form resin, (3) a method in which an anti-allergen agent is molded into high concentration pellet form using a wax, and the resulting pellet-form molding is then combined with a pellet-form resin, (4) a method in which a paste-form composition is prepared by dispersion-mixing an anti-allergen agent in a highly viscous liquid such as a polyol, and this paste is then combined with a pellet-form resin, etc.

Molding of the above-mentioned resin composition may employ any known molding technique and mechanical equipment commensurate with the properties of various types of resins, and preparation may be carried out easily by a method involving mixing, incorporating, or kneading while heating and applying pressure or vacuum at an appropriate temperature or pressure; specific procedures therefor may employ standard methods, and moldings can be obtained in various forms such as clump form, sponge form, film form, sheet form, thread form, pipe form, or a composite form thereof. When the anti-allergen agent/resin composition solids content ratio by weight in a resin composition containing the anti-allergen agent of the present invention is at least 10/90, a clear effect can easily be exhibited. Furthermore, in terms of economic reasons, moldability of the resin composition, or physical properties and texture of a molding not being degraded, it is preferably no greater than 50/50. Therefore, the anti-allergen agent/resin composition solids content ratio by weight in a resin composition containing the anti-allergen agent of the present invention is preferably 10/90 to 50/50, and more preferably 20/80 to 40/60.

With regard to the configuration of use of the anti-allergen agent of the present invention, other than the above-mentioned composition, resin composition, and resin molding, it may be used as it is, as a mixture with another component as appropriate, or as a composite with another material, according to the intended application in which it is necessary to suppress an allergen. For example, it may be used in any form such as powder form, powder dispersion form, granular form, aerosol form, or liquid form.

The anti-allergen agent of the present invention may be utilized in various fields where suppression of an allergen is required, that is, interior goods, bedding, filters, furniture, vehicle interior goods, fiber products, house building products, paper products, toys, leather products, toiletry products, cosmetics, and other products. Examples thereof include interior goods such as carpets, curtains, wallpaper, tatami, screen paper, floor wax, and calendars, bedding such as duvets, beds, sheets, pillows, and pillow covers, filters for air cleaners or air conditioners, furniture such as sofas and chairs, vehicle interior goods such as child seats and passenger seats, dustbags for vacuum cleaners, clothing, masks, soft toys, and kitchen goods, but the examples are not limited thereto.

Compared with existing anti-allergen agents, the anti-allergen agent of the present invention not only exhibits high anti-allergen activity but also exhibits excellent heat resistance due to it being an inorganic substance, has little coloration or change in color, and is not leached out by water, and it therefore has durability. It can impart excellent anti-allergen properties to various products by simple processing methods.

EXAMPLES

The present invention is explained in further detail by reference to Examples below, but the Examples should not be construed as limiting the present invention.

The average particle size of an inorganic powder described in the Examples means median diameter on a volumetric basis obtained by ultrasonically dispersing in deionized water and measuring by means of a laser diffraction particle size distribution meter, % means mass % unless otherwise specified, and the units of % for the percentage allergen inactivation are those obtained from <Equation 1>.

With regard to measurement of the concentration of acid sites, 0.5 g samples of an inorganic powder were placed in 20 mL sample vials, 10 mL of benzene was added to each thereof, and the vials were lightly shaken. 20 stepped amounts of 0.1 N n-butylamine were added thereto, and stirring was carried out by an agitator. 24 hours thereafter, 0.5 mL of a 0.1% methyl red solution diluted with benzene was added thereto, and change in color of the methyl red was examined visually. The amount of n-butylamine added that was the largest amount of n-butylamine added where no change in color of methyl red was observed was defined as the amount of base that had reacted with the acid sites, and was expressed as the concentration of acid sites (mmol/g).

Measurement of acid strength was carried out by weighing 0.1 g of a sample in a test tube, adding 2 mL of benzene and two drops of a 0.1% benzene solution of an indicator (0.1% ethanol solution for crystal violet), lightly shaking so as to mix them, and examining for change of color. Since the acid strength can be considered to be equal to or less than the highest acid strength for which change in color of the indicator is observed (lowest pKa value) and greater than the lowest acid strength for which change in color of the indicator is not observed (highest pKa), this range was recorded as the pKa value. The indicators used were methyl red (pKa=4.8), 4-phenylazo-1-naphthylamine (pKa=4), dimethyl yellow (pKa=3.3), 4-phenylazo-diphenylamine (pKa=1.5), crystal violet (pKa=0.8), dicinnamylacetone (pKa=−3), benzalacetophenone (pKa=−5.6), and anthraquinone (pKa=−8.2).

With regard to the water content of an inorganic powder, about 5 g of a sample was weighed (weighed to a precision of 0.1 mg) into an aluminum cup that had been taken to constant mass in a dryer at 250° C. for 1 hour, was dried in a dryer at 250° C. for 2 hours, and was then weighed again (weighed to a precision of 0.1 mg), the water content of the inorganic powder being defined by the quotient, expressed as a %, obtained by dividing the decrease due to drying by the mass before drying.

Anti-allergen effects were evaluated by a sandwich ELISA method employing Dermatophagoides farinae allergen (allergen generally called Derf2) and Cryptomeria japonica pollen allergen (allergen generally called Cryj1). The test procedure when Dermatophagoides farinae allergen was used was as follows. Antibody-coated wells were prepared by a standard method using a Dermatophagoides farinae allergen (Derf2)-specific antibody (15E11 antibody, Asahi Breweries, Ltd.). 3 mg of a sample was weighed, and 500 μL of Dermatophagoides farinae allergen (Derf2) prepared at 40 ng/mL using an antigen diluent was added thereto. The mixture was stirred well so as to contact the sample with the allergen and was then subjected to centrifugation, and the supernatant was collected, added to 15E11 antibody-coated wells that had been treated with a blocking agent, and allowed to stand at room temperature. After 1 hour, the sample was discarded, each well was washed with washing buffer, 200 ng/mL of horseradish peroxidase-labeled anti-Derf2 monoclonal antibody 13A4PO (Asahi Breweries, Ltd.) that had been diluted with washing buffer was added to each well, and the wells were allowed to stand at room temperature. After 1 hour, the antibody liquid was discarded, each well was washed with washing buffer, a substrate liquid was added to each well, and the wells were allowed to stand at room temperature. After 5 minutes, 2N sulfuric acid was added so as to stop the reaction, and the absorbance at 490 nm was measured. The results were expressed as percentage allergen inactivation of various samples by determining the relationship between amount of allergen and absorbance from an evaluation carried out without using a sample, determining the amount of allergen remaining from the absorbance obtained when evaluating various types of samples, and calculating from <Equation 1> above.

The test procedure for the sandwich ELISA method when Cryptomeria japonica pollen allergen was used was as follows. Antibody-coated wells were prepared by a standard method using a Cryptomeria japonica pollen allergen (Cryj1)-specific antibody (Anti-Cryj1mAb013, Seikagaku Corporation). 3 mg of a sample was weighed, and 500 μL of Cryptomeria japonica pollen allergen (Cryj1) prepared at 10 ng/mL using an antigen diluent was added thereto. The mixture was stirred well so as to contact the sample with the allergen and was then subjected to centrifugation, and the supernatant was collected, added to Anti-Cryj1mAb013 antibody-coated wells that had been treated with a blocking agent, and allowed to stand at room temperature. After 1 hour, the sample was discarded, each well was washed with washing buffer, 250 ng/mL of horseradish peroxidase-labeled anti-Cryj1 monoclonal antibody 053 (Seikagaku Corporation) that had been diluted with washing buffer was added to each well, and the wells were allowed to stand at room temperature. After 2 hours, the antibody liquid was discarded, each well was washed with washing buffer, a substrate liquid was added to each well, and the wells were allowed to stand at room temperature. After 5 minutes, 2N sulfuric acid was added so as to stop the reaction, and the absorbance at 490 nm was measured. The results were expressed as percentage allergen inactivation of various types of samples by calculating from Equation 1 by the same method as for Dermatophagoides farinae allergen.

With regard to the pH of an aqueous dispersion of an inorganic powder, the inorganic powder was dispersed in ion-exchanged water in a beaker at 5 wt %, and the pH after stirring at 25° C. for 5 min. by means of a stirrer was measured using a glass electrode pH meter.

With regard to a test for confirming change in color of a resin molding, an inorganic powder was added at 2 wt % to a polypropylene powder, and a plate was molded at 220° C. using an injection molding machine. The degree of coloration of the plate thus obtained was examined visually.

With regard to a metal corrosivity test, a test piece made of iron (width/length/thickness=20/80/2 mm) was first prepared and the surface was washed with acetone. The test piece made of iron and a 5 wt % aqueous dispersion of an inorganic powder were placed in a glass test tube having a diameter of 30 mm, and it was set in a heating block adjusted to 60° C. 24 hours thereafter, the test piece was taken out, immersed in distilled water, ultrasonically washed for 5 min., then dried in a dryer at 50° C. for 30 min., and presence or absence of rust on the test piece was examined visually.

The anti-allergen effect of a processed fiber product was evaluated as percentage anti-allergen inactivation from Equation 1 above by using Cryptomeria japonica pollen allergen (Cryj1) as the allergen, placing 25 cm² of the fiber in a reclosable plastic bag, contacting the sample with 1 mL of a 100 ng/mL allergen solution for 1 hour, then centrifuging the contacted liquid, collecting a supernatant, measuring the absorbance by evaluation involving the same ELISA method as for an inorganic powder, and comparing with the absorbance when no sample was used.

The anti-allergen effect of a resin-kneaded film was evaluated as percentage anti-allergen inactivation from Equation 1 above by using Cryptomeria japonica pollen allergen (Cryj1) as the allergen, placing 25 cm² of the film in a reclosable plastic bag, contacting the sample with 1 mL of a 10 ng/mL allergen solution for 1 hour, then centrifuging the contacted liquid, collecting a supernatant, measuring the absorbance by evaluation involving the same ELISA method as for an inorganic powder, and comparing with the absorbance when no sample was used.

The anti-allergen effect of a film processed with an acrylic UV-curing paint was evaluated as percentage anti-allergen inactivation from Equation 1 above by using Cryptomeria japonica pollen allergen (Cryj1) as the allergen, placing 25 cm² of the film in a reclosable plastic bag, contacting the sample with 1 mL of a 10 ng/mL allergen solution for 3 hours, then centrifuging the contacted liquid, collecting a supernatant, measuring the absorbance by evaluation involving the same ELISA method as for an inorganic powder, and comparing with the absorbance when no sample was used.

Example 1 Amorphous Magnesium Silicate

An amorphous magnesium silicate (SiO₂/MgO=1.3) was obtained by filtering a precipitate obtained using as starting materials magnesium sulfate and water glass, washing it with water, drying, and grinding. The amorphous magnesium silicate thus obtained was subjected to measurement of average particle size, water content, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Example 2 α-Type Zirconium Phosphate

An α-type zirconium phosphate powder was obtained by adding a 15% zirconium oxychloride aqueous solution to a 75% phosphoric acid aqueous solution, carrying out aging at 120° C. for 12 hours, then filtering a precipitate, washing it with water, drying, and grinding. The α-type zirconium phosphate thus obtained was subjected to measurement of average particle size, water content, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Example 3 Activated Titanium Oxide

An activated titanium oxide was prepared by filtering a precipitate obtained using as starting materials titanyl sulfate and oxalic acid, drying, calcining at 500° C., and then grinding. The titanium oxide thus obtained was subjected to measurement of average particle size, water content, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Example 4 Activated Kaolin

A commercial activated kaolin (Galleon Earth SH, Mizusawa Industrial Chemicals, Ltd.) was subjected to measurement of average particle size, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 1 Amorphous Magnesium Silicate

An amorphous magnesium silicate (SiO₂/MgO=3.9) was obtained by filtering a precipitate obtained using as starting materials magnesium sulfate and water glass, washing it with water, drying, and grinding. The crystalline magnesium silicate thus obtained was subjected to measurement of average particle size, water content, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 2 γ-Type Zirconium Phosphate

A γ-type zirconium phosphate was obtained by adding a zirconium carbonate aqueous solution to a 75% phosphoric acid aqueous solution, carrying out refluxing by heating at 98° C. for 24 hours, then filtering a precipitate, washing it with water, drying, and grinding. The γ-type zirconium phosphate thus obtained was subjected to measurement of average particle size, water content, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 3 NASICON-Type Zirconium Phosphate

A NASICON-type zirconium phosphate was obtained by adding oxalic acid and a 75% phosphoric acid aqueous solution to a zirconium oxychloride aqueous solution, adjusting the pH to 2.7 using sodium hydroxide, then carrying out refluxing by heating at 98° C. for 12 hours, then filtering a precipitate, washing it with water, drying, and grinding. The NASICON-type zirconium phosphate thus obtained was subjected to measurement of average particle size, water content, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 4 Titanium Oxide

A commercial titanium oxide (MC-50, Ishihara Sangyo Kaisha Ltd.) was subjected to measurement of average particle size, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 5 Activated Alumina

A commercial activated alumina (GNDY-2, Mizusawa Industrial Chemicals, Ltd.) was subjected to measurement of average particle size, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 6 Silica-Alumina

A silica-alumina was prepared by stirring water glass and aluminum nitrate as starting materials at 98° C., calcining a precipitate obtained at 400° C., and then grinding. The silica-alumina thus obtained was subjected to measurement of average particle size, water content, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 7 Aluminum Phosphate

A commercial aluminum phosphate (K-WHITE 105, Tayca Corporation) was subjected to measurement of average particle size, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

Comparative Example 8 Hydrotalcite

A commercial hydrotalcite (HT-P, Sakai Chemical Industry Co., Ltd.) was subjected to measurement of average particle size, acid strength, and mite allergen inactivating effect and Cryptomeria japonica pollen allergen inactivating effect by the ELISA method, and the results are shown in Table 1. Furthermore, the results of measurement of color tone, pH of a 5 wt % aqueous dispersion, coloration of a PP plate, and metal corrosivity are shown in Table 2.

TABLE 1 Average Acid site Percentage allergen particle Water concentration inactivation (%) Inorganic powder size (μm) content % (mmol/g) pKa Derf2 Cryj1 Ex. 1 Amorphous 5.5 10 0.07 0.8 to 1.5 >99 >99 magnesium silicate Ex. 2 α-Type zirconium 0.2 5 0.01 −8.2 to −5.6 99 99 phosphate Ex. 3 Activated titanium 0.01 6.5 0.02 4.0 to 3.3 99 99 oxide Ex. 4 Activated kaolin 5.2 7 0.002 <−8.2 99 99 Comp. Ex. 1 Amorphous 2.8 6.8 <0.001 0.8 to 1.5 <10 <10 magnesium silicate Comp. Ex. 2 γ-Type zirconium 1 3.1 <0.001 −8.2 to −5.6 45 40 phosphate Comp. Ex. 3 NASICON-type 1 0.4 <0.001 −8.2 to −5.6 35 20 zirconium phosphate Comp. Ex. 4 Commercial 0.02 0.4 <0.001 −5.6 to −3.0 85 65 titanium oxide Comp. Ex. 5 Activated alumina 0.4 1.8 <0.001 0.8 to 1.5 <10 <10 Comp. Ex. 6 Silica-alumina 5.4 9 <0.001 0.8 to 1.5 30 25 Comp. Ex. 7 Aluminum 0.3 6.9 <0.001 4.0 to 3.3 <10 <10 phosphate Comp. Ex. 8 Hydrotalcite 4.4 4.8 <0.001   >4.8 <10 <10

TABLE 2 Color Coloration when Metal Component tone pH kneading resin corrosivity Ex. 1 Amorphous magnesium White 8 None None silicate Ex. 2 α-Type zirconium White 3 None None phosphate Ex. 3 Activated titanium oxide White 6 None None Ex. 4 Activated kaolin White 2 Black discoloration Rusted Comp. Ex. 1 Amorphous magnesium White 8 None None silicate Comp. Ex. 2 γ-Type zirconium White 3 None None phosphate Comp. Ex. 3 NASICON-type zirconium White 4 None None phosphate Comp. Ex. 4 Commercial titanium White 2 Brown discoloration Rusted oxide Comp. Ex. 5 Activated alumina White 5 None None Comp. Ex. 6 Silica-alumina White 6 None None Comp. Ex. 7 Aluminum phosphate White 6 None None Comp. Ex. 8 Hydrotalcite White 9 Yellow discoloration None

From the results in Table 1, all of the inorganic powders having a concentration of acid sites of 0.001 mmol/g or higher of the present invention showed a percentage mite allergen inactivation of 99% or greater. In particular, the amorphous magnesium silicate having a concentration of acid sites of 0.07 mmol/g exhibited the effect of the percentage allergen inactivation being greater than 99%, and was truly excellent as an anti-allergen agent.

Furthermore, in the case of Cryptomeria japonica pollen allergen, as in the case of mite allergen, the anti-allergen agent of the present invention exhibited a high percentage allergen inactivation and was truly excellent as an anti-allergen agent. On the other hand, in the Comparative Examples, where the concentration of acid sites was equal to or less than 0.001, hardly any anti-allergen activity was exhibited.

Moreover, from the results of Table 2, the dispersions of Example 4 and Comparative Example 4 had a pH for a 5 wt % dispersion of less than 3 and exhibited metal corrosivity.

Example 7 Evaluation of Anti-Allergen Activity of Fiber-Fixed Example 1

The amorphous magnesium silicate that was the inorganic substance of Example 1 and an acrylic emulsion binder (NW-7060, Toagosei Co., Ltd., solids content 50%,) were mixed at a solids content ratio by mass of 2:1 and applied to a fabric (components: cotton/acrylic fiber=1/1) by immersion for 5 min. and then dried at 120° C. for 30 min., thus preparing an anti-allergen fabric having an amount of amorphous magnesium silicate fixed of 1 g/m². The Cryptomeria japonica pollen allergen inactivating effect of the anti-allergen fabric was measured, and the result is shown in Table 3.

Example 8 Evaluation of Anti-Allergen Activity of Fiber-Fixed Example 1

The amorphous magnesium silicate that was the inorganic substance of Example 1 and (NW-7060, Toagosei Co., Ltd., solids content 50%,) were mixed at a solids content ratio by mass of 2:1 and applied to a fabric (components: cotton/acrylic fiber=1/1) by immersion for 5 min. and then dried at 120° C. for 30 min., thus preparing an anti-allergen fabric having an amount fixed of 2 g/m². The Cryptomeria japonica pollen allergen inactivating effect of the anti-allergen fabric was measured, and the result is shown in Table 3.

Comparative Example 9 Evaluation of Anti-Allergen Activity when Example 1 was not Fixed to Fiber

A comparative fabric was prepared by the same processing method as in Example 7 without using the amorphous magnesium silicate that was the inorganic substance of Example 1. The Cryptomeria japonica pollen allergen inactivating effect of the comparative fabric was measured, and the result is shown in Table 3

TABLE 3 Inorganic substance and Percentage allergen amount fixed inactivation (%) Ex. 7 Magnesium silicate 1 g/m² 97 Ex. 8 Magnesium silicate 2 g/m² >99 Comp. Ex. 9 Binder only 15

From the results in Table 3, it was found that the anti-allergen processed fabrics to which the amorphous magnesium silicate of Example 1 was attached exhibited a percentage allergen inactivation of greater than 99%. Therefore, the performance of the anti-allergen products formed by post-processing a fiber with the inorganic substance of the present invention was excellent.

Example 9 Evaluation of Heat Resistance of Fiber-Fixed Example 1

An anti-allergen fabric was prepared by the same method as in Example 7 and subjected to heating at 120° C. for 100 hours, and the Cryptomeria japonica pollen allergen inactivating effect and color change of the anti-allergen fabric were then measured, the results thereof being shown in Table 4.

Example 10 Evaluation of Heat Resistance of Fiber-Fixed Example 1

An anti-allergen fabric was prepared by the same method as in Example 8 and subjected to heating at 120° C. for 100 hours, and the Cryptomeria japonica pollen allergen inactivating effect and color change of the anti-allergen fabric were then measured, the results thereof being shown in Table 4.

TABLE 4 Percentage allergen inactivation (%) Change in color Ex. 9 96 No change in color Ex. 10 >99 No change in color

From the results of Table 4, since the anti-allergen processed fabric to which the amorphous magnesium silicate of Example 1 was attached exhibited a sufficiently high percentage allergen inactivation even when heat was applied for a long time and in addition exhibited hardly any change in color, the anti-allergen product formed by post-processing a fiber with the inorganic substance of the present invention had excellent heat resistance.

Example 11 Evaluation of Water Resistance of Fiber-Fixed Example 1

An anti-allergen fabric was prepared by the same method as in Example 7 and placed in a plastic container, ion-exchanged water was added thereto, the container was shaken at 25° C. for 16 hours, the anti-allergen fabric was dried at 120° C. for 30 min., and the Cryptomeria japonica pollen allergen inactivating effect thereof was measured, the results being shown in Table 5.

Example 12 Evaluation of Water Resistance of Fiber-Fixed Example 1

An anti-allergen fabric was prepared by the same method as in Example 8 and placed in a plastic container, ion-exchanged water was added thereto, the container was shaken at 25° C. for 16 hours, the anti-allergen fabric was dried at 120° C. for 30 min., and the Cryptomeria japonica pollen allergen inactivating effect thereof was measured, the results being shown in Table 5.

TABLE 5 Percentage allergen inactivation (%) Ex. 11 97 Ex. 12 >99

From the results of Table 5, the anti-allergen processed fabric to which the amorphous magnesium silicate of Example 1 was attached exhibited a sufficiently high percentage allergen inactivation even after being treated with water. Therefore, the anti-allergen product formed by post-processing a fiber with the inorganic substance of the present invention had excellent water resistance as well.

Example 13 Evaluation of Anti-Allergen Activity of Resin-Kneaded Example 1

The amorphous magnesium silicate that was the inorganic substance of Example 1 and powdered polypropylene were mixed at a solids content ratio by mass of 10:90 and thermally pressed at 220° C., thus preparing an anti-allergen film having a film thickness of 0.2 mm. The results of measuring the Cryptomeria japonica pollen allergen inactivating effect of the anti-allergen film are shown in Table 6.

Example 14 Evaluation of Anti-Allergen Activity of Resin-Kneaded Example 1

The amorphous magnesium silicate that was the inorganic substance of Example 1 and powdered polypropylene were mixed at solids content ratio by mass of 20:80 and thermally pressed at 220° C., thus preparing an anti-allergen film having a film thickness of 0.2 mm. The results of measuring the Cryptomeria japonica pollen allergen inactivating effect of the anti-allergen film are shown in Table 6.

Comparative Example 10 Evaluation of Anti-Allergen Activity when Resin was not Kneaded with Example 1

A comparative film was prepared by the same processing method as in Example 13 without using the amorphous magnesium silicate that was the inorganic substance of Example 1. The results of measuring the Cryptomeria japonica pollen allergen inactivating effect of the comparative film are shown in Table 6.

TABLE 6 Inorganic substance and Percentage allergen amount added inactivation (%) Ex. 13 Magnesium silicate 10 wt % 50 Ex. 14 Magnesium silicate 20 wt % >99 Comp. Ex. Film only 0 10

From the results of Table 6, the anti-allergen processed film that had been kneaded with the amorphous magnesium silicate of Example 1 exhibited a high percentage allergen inactivation by the addition of 20 wt % thereof. Therefore, the anti-allergen product formed by kneading a resin with the inorganic substance of the present invention had excellent performance.

Example 15 Evaluation of Anti-Allergen Activity of UV-Curing Resin-Processed Example 1

The amorphous magnesium silicate that was the inorganic substance of Example 1 and an acrylic UV-curing paint (without solvent) were mixed at a solids content ratio by mass of 15:85, the mixture was applied to a PET film (Lumirror T60-50, Toray) at a thickness of 15 μm using a bar coater, and irradiated with UV using a high-pressure mercury lamp (intensity 60 W/cm) from a distance of 25 cm at a conveyor speed of 3.7 m/min to thus cure the composition, thereby preparing an anti-allergen film. The result of measuring the Cryptomeria japonica pollen allergen inactivating effect of the anti-allergen film is shown in Table 7.

Example 16 Evaluation of Anti-Allergen Activity of UV-Curing Resin-Processed Example 1

The amorphous magnesium silicate that was the inorganic substance of Example 1 and an acrylic UV-curing paint were mixed at a solids content ratio by mass of 30:70, the mixture was applied to a PET film (Lumirror T60-50, Toray) at a thickness of 15 μm using a bar coater, and irradiated with UV using a high-pressure mercury lamp (intensity 60 W/cm) from a distance of 25 cm at a conveyor speed of 3.7 m/min to thus cure the composition, thereby preparing an anti-allergen film. The result of measuring the Cryptomeria japonica pollen allergen inactivating effect of the anti-allergen film is shown in Table 7.

Comparative Example 11 Evaluation of Anti-Allergen Activity of Film Processed with Acrylic UV-Curing Paint when Example 1 was not Fixed Thereto

A comparative film was prepared by the same processing method as in Example 15 without using the amorphous magnesium silicate that was the inorganic substance of Example 1. The result of measuring the Cryptomeria japonica pollen allergen inactivating effect of the comparative film is shown in Table 7.

TABLE 7 Inorganic substance and Percentage allergen amount added inactivation (%) Ex. 15 Magnesium silicate 15 wt % 50 Ex. 16 Magnesium silicate 30 wt % 80 Comp. Ex. Resin coating only 20 11

From the results of Table 7, the anti-allergen film that had been coated with the amorphous magnesium silicate of Example 1 by UV curing exhibited a high percentage anti-allergen inactivation. Therefore, the anti-allergen product whose surface was processed by UV curing with the inorganic substance of the present invention had excellent performance.

Example 17

In order to carry out an evaluation of anti-allergen properties in an actual application environment, the amorphous magnesium silicate that was the inorganic substance and an acrylic emulsion binder (NW-7060, Toagosei Co., Ltd., solids content 50 wt %) were mixed at a solids content ratio by mass of 2:1 by the method in accordance with Example 8, and a bath towel (155 cm×70 cm, component: cotton) was immersed therein for 5 min. and then dried at 120° C. for 60 min., thus preparing an anti-allergen fabric (bath towel) having an amount fixed of 2 g/m².

On a fine day on which Cryptomeria japonica pollen was released, the bath towel was dried under the sun for 6 hours on an outdoor dryer, thus adsorbing thereon Cryptomeria japonica pollen floating in the environment. After allowing to stand overnight, the entire surface of the bath towel was vacuumed using a vacuum cleaner having a nonwoven fabric set therein, thus collecting the allergen by vacuum on the nonwoven fabric. The allergen on the nonwoven fabric was extracted with 10 mL of an antigen dilution liquid (0.1% BSA+PBS buffer), and the amount of Cryptomeria japonica pollen allergen (Cryj1) collected was measured by the ELISA method, thus giving an amount of allergen collected. Since the amount of natural Cryptomeria japonica pollen released changes greatly according to the weather or the day, on other fine days spaced by at least three days, the same adsorption test was carried out three times, and the results of measuring the amount of allergen collected are shown in Table 8. 1st, 2nd, and 3rd day in Table 8 mean that the adsorption test was carried out on three different days.

Comparative Example 12

A bath towel of Comparative Example 12 was prepared in the same manner as in Example 17 except that only a binder that did not contain the amorphous magnesium silicate was used, and Cryptomeria japonica pollen floating in the environment was similarly adsorbed thereon at the same place on the same days as for Example 17. The results of measuring the amount of allergen collected are shown in Table 8.

TABLE 8 Amount of allergen recovered (ng) 1st day 2nd day 3rd day Ex. 17 Magnesium silicate present 200 <10 65 Comp. Ex. 12 Binder only 795 130 145

Since for comparisons on the same day, the amount of Cryptomeria japonica pollen attached to the bath towel of Example 17 can be considered to be at the same level as that of the bath towel of Comparative Example 12, the result for the amount of Cryptomeria japonica pollen allergen collected from the bath towel of Example 17, to which the amorphous magnesium silicate was fixed, being very low compared with the bath towel of Comparative Example 12, which did not have the amorphous magnesium silicate, suggests that the attached Cryptomeria japonica pollen allergen was inactivated by the amorphous magnesium silicate on the bath towel of Example 17.

INDUSTRIAL APPLICABILITY

In accordance with use of the anti-allergen agent of the present invention, it becomes possible to impart a function of inactivating allergens derived from pollen, mites, etc. to a material related to a human living space such as a fiber product or a housing material, and an anti-allergen product can be produced. 

1.-8. (canceled)
 9. An anti-allergen agent comprising an inorganic powder having a concentration of acid sites with a pKa of no greater than 4.8 of at least 0.001 mmol/g but no greater than 10 mmol/g.
 10. The anti-allergen agent according to claim 9, wherein the inorganic powder has a median diameter, measured by a laser particle size distribution analyzer and calculated on a volumetric basis, of at least 0.01 μm but no greater than 50 μm.
 11. The anti-allergen agent according to claim 9, wherein the inorganic powder has a pH as a 5 wt % aqueous dispersion of at least 3 but no greater than
 9. 12. The anti-allergen agent according to claim 9, wherein the inorganic powder is at least one selected from an amorphous magnesium silicate, an α-type zirconium phosphate, and an activated titanium oxide.
 13. The anti-allergen agent according to claim 9, wherein the inorganic powder is an amorphous magnesium silicate.
 14. The anti-allergen agent according to claim 9, wherein the inorganic powder has a concentration of acid sites with a pKa of no greater than 4.8 of at least 0.01 mmol/g but no greater than 10 mmol/g.
 15. The anti-allergen agent according to claim 9, wherein the water content of the inorganic powder is at least 0.5 wt %.
 16. A method for inactivating an allergen comprising: a step of preparing an anti-allergen agent, and a step of directly contacting the anti-allergen agent with an allergen, wherein the anti-allergen agent comprising an inorganic powder having a concentration of acid sites with a pKa of no greater than 4.8 of at least 0.001 mmol/g but no greater than 10 mmol/g.
 17. The method for inactivating an allergen according to claim 16, wherein the inorganic powder has a median diameter, measured by a laser particle size distribution analyzer and calculated on a volumetric basis, of at least 0.01 μm but no greater than 50 μm.
 18. The method for inactivating an allergen according to claim 16, wherein the inorganic powder has a pH as a 5 wt % aqueous dispersion of at least 3 but no greater than
 9. 19. The method for inactivating an allergen according to claim 16, wherein the inorganic powder is at least one selected from an amorphous magnesium silicate, an α-type zirconium phosphate, and an activated titanium oxide.
 20. The method for inactivating an allergen according to claim 16, wherein the inorganic powder is an amorphous magnesium silicate.
 21. The method for inactivating an allergen according to claim 16, wherein the inorganic powder has a concentration of acid sites with a pKa of no greater than 4.8 of at least 0.01 mmol/g but no greater than 10 mmol/g.
 22. The method for inactivating an allergen according to claim 16, wherein the water content of the inorganic powder is at least 0.5 wt %.
 23. A coating composition comprising the anti-allergen agent according to claim 9 and a binder or a paint.
 24. The coating composition according to claim 23, wherein it has a pH of at least 3 but no greater than
 9. 25. An anti-allergen product processed using the coating composition according to claim
 23. 26. An anti-allergen fabric processed using the coating composition according to claim
 23. 